Manufacture of cyclopentadienyl nickel nitrosyl compounds



United States Patent 3,088,963 MANUFACTURE OF CYCLGPENTADIENYL NICKEL NITRUSYL COMPOUNDS Michael Dubeck, Royal Oak, Mich, assignor to Ethyl Corporation, New York, N.Y., a corporation of Delaware N0 Drawing. Filed Sept. 12, 1960, er. No. 55,181 r 6 Claims. (Cl. 260-439) This invention relates to novel organometallic compounds and a process for their preparation. More specifically, this invention relates to cyclomatic nickel nitrosyl compounds.

It is an object of this invention to provide a novel process for the preparation of cyclomatic nickel nitrosyl compounds. A further object is to provide novel compounds produced by this process. Additional objects will become apparent from a reading of the specification and claims which follow.

The objects of this invention are accomplished by providing a process in which compounds having the formula QCECQ' -CyNiNiCy' are reacted with a nitrosylating agent to form compounds having the formulae CyNiNO and Cy'NiNO. The compounds, CQECQ'-CyN-iNiCy', are fully described in my prior US. application Serial No. 852,216, filed November 12, 1959. As shown in that application, these compounds are believed to have the structural formula as follows:

Cy Infin Cy In this formula, Q and Q represent either hydrogen or univalent hydrocarbon radicals containing from one to about 10 carbon atoms. Cy and Cy represent cyclomatic hydrocarbon groups which donate five electrons to the nickel atoms for bonding. By viture of the electrons donated to each of the nickel atoms from the cyclomatic hydrocarbon groups, the acetylene molecule and the other nickel atom, each of the nickel atoms achieves the inert gas electron configuration of krypton.

The rcyolomatic hydrocarbon groups, designated :by the symbols Cy and Cy in the above formula, may be the same or diiferent and are cyclopentadienyl-type hydrocarbon radicals. By this, it is meant that the radical contains the cyclopent-adienyl moiety. In general, such cyolomatic hydrocarbon groups can be represented by the formulae:

1 3 114 Ri l u R3 R1 Rrg R4 RT- wherein the R's are selected from the group consisting of hydrogen and univalent hydrocarbon radicals.

A preferred class of cyclomatic radicals suitable in the practice of my invention are those which contain from five to about 13 carbon atoms. These are exemplified by cyclopentadienyl, indenyl, methylcyclopentadienyl, propylcyclopentadienyl, diethylcyclopentadienyl, phenylcyclopentadienyl, tert-butyl cyclopentadienyl, p-ethylphenyl cyclopentadienyl, 4-tert butyl indenyl and the like. The compounds which yield these radicals are preferred as they are the more readily available cyclomatic compounds, and the compounds of my invention containing these radicals have the more desirable physical characteristics which render them of superior utility.

As shown in the above formula, the bridging acetylenetype molecule is believed to be bonded to both of the nickel atoms in forming the compounds of my invention. As visualized, the triple bond in the bridging acetylenic 3,38,%3 Patented May 7, 1963 compound is reduced to a single bond thus making four electrons available for bonding to the two nickel atoms. Each of the carbon atoms on either side of the triple bond is thereby bonded to each of the nickel atoms. The actual configuration of the bridging acetylenic molecule is believed to be approximately at right angles to the plane in which the two inter-connected nickel atoms lie. This is shown in the above formula by means of the dotted lines indicating bonding of the carbon atom which is behind the plane of the paper to the two nickel atoms illustrated as lying in the plane of the paper. The other carbon atom which is bonded to the two nickel atoms is depicted as lying in front of the plane of the paper. Thus, the bonds between this carbon atom and the two nickel atoms are drawn as solid lines.

The substituent groups Q and Q, as shown in the above formula, may be the same or different and are hydrogen or univalent hydrocarbon groups containing from one to about 10 carbon atoms. Q and Q are preferably alkyl groups such as methyl, ethyl, pnopyl, butyl, amyl, octyl or decyl, including normal alkyls or branched chain alkyls. Preferably, Q and Q, if an alkyl group, contains from one to about six carbon atoms since alkyl radicals within this range impart desirable physical properties to the compounds of my invention.

Q and Q may also be an aryl radical, either a cfused or single ring, such as phenyl, tolyl, xylyl, naphthyl or the like. In addition, Q and Q may be hydrocarbon groups containing unsaturated double bonds such as alkenyl or cycloalkenyl radicals. Typical of such radicals are butenyl, pentenyl, hexenyl, nonenyl, cyclohexenyl, cyclopentenyl and the like. In addition, the Q groups may be alkaryl radicals, aralkyl radicals, and cycloalkyl radicals containing up to about 10 carbon atoms. Typical of such radicals are benzyl, phenylethyl, phenylpropy-l, phenylbutyl, cyclohexyl, cyclopentyl, cycloheptyl, cyclodecyl, p ethylphenyl, m-butylphenyl, p-methylphenyl and the like.

Although the Q groups, as defined above, are univalent hydrocarbon radicals or hydrogen, these groups may be substituted with polar substituents which preferably should be separated by at least two carbon atoms from the triple acetylenic bond to avoid cumbersome side reactions. Typical acetylenic compounds containing such non-reactive nonehydrocanbon substituent groups are perhalo butynes, propargyl alcohol, ethynyl cyclohexanol, Ibeta carboxy esters of the butynes, pentynes, hexynes, and heptynes, S-inethoxy pentyne-l, and the like.

The reactant, Qcz-CQ-CyNiNiCy, as described above, is reacted with a nitrosylating agent according to the process of my invention. A variety of nitrosylating agents such as, for example, nitric oxide, an alkali metal nitrite such as sodium or potassium nitrite, or a nitrososubstituted aromatic compound such as N-methyl-N- nitroso-p-toluene sulfonamide may be employed. Preferably, however, the nitrosylating agent is nitric oxide since it is comparatively cheap, readily available and, as a gas, can be intimately mixed with the nickel reactant and thereby give an especially high yield of product. My process can be carried out at temperatures from about zero to about C. Preferably, however, my process is carried out between about 20 to about 30 C. since within this temperature range yields are maximized, and undesirable side reactions are minimized.

My process may be carried out under pressure if desired. In general, however, it goes well at atmospheric pressure. Although not essential, it is desirable to agitate the reaction mixture since this insures an even reaction rate. In some instances, it may be desirable to employ in the reaction system a blanketing atmosphere of an inert gas. The function of the inert gas is to shield the reaction mixture from oxidation and thereby prevent oxi- 3 dation of the reactants or products. Typical of such inert gases are nitrogen, argon, crypton and neon. Nitrogen is preferred since it is cheap and readily available. In general, however, the nitric oxide reactant, which is a gas, serves as a blanketing atmosphere and thereby eliminates the need for an inert gas atmosphere.

In conducting my process, it is preferable to employ excess quantities of the nitrosylating agent, e.g. nitric oxide. The nitrosylating agent is generally considerably cheaper than the nickel reactant, and its use in excess quantity assures consumption of the nickel reactant in the process.

The products formed in my process, which are cyclomatic nickel nitrosyl compounds having the formulae, CyNiNO and CyNiNO, are readily separated from the reaction mixture by conventional means. Typical means of separation are chromatography, fractional distillation and crystallization.

A preferred form of my invention involves reaction between nitric oxide and th: compound, acetylene bis (cyclopentadienyl nickel). This form of my invention is preferred for several reasons. First, it employs reactants which are relatively cheap and readily available; the acetylene bis(cyclopentadienyl nickel) compound is prepared by reaction of acetylene and nickelocene. Second, it produces as the product the compound, cyclopentadienyl nickel nitrosyl which has demonstrated utility both as a primary and supplemental antiknock.

My process is generally carried out in the presence or a solvent. In general, any unreactive solvent in which the acetylenic bis(cyclomatic nickel) reactant is fairly soluble may be employed. Typical of such solvents are high boiling saturated hydrocarbons such as n-octane, n-dccane, and other paraflinic hydrocarbons having up to about 20 carbon atoms such as eicosane, pentadecane and the like. Also applicable are aromatic solvents such as benzene, toluene, mesitylene, and the like. Typical ether solvents are ethyl octyl ether, ethyl hexyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, trioxane, tetrahydrofuran, ethylene glycol dibutyl ether and the like. Ester solvents which may be employed include pentyl butanoate, ethyl decanoate, ethyl hexanoate, and the like. Silicone oils such as the dimethyl polysiloxanes, bis(chlorophenyl) polysiloxanes, hexaproplydisilane, and diethf 'ldipropyldiphenyldisilane may also be employed. Other ester solvents are those derived from succinic, glutaric, adipic, pimelic, suberic, azelaic, and sebacic acids. Specific examples of such esters are di-(2- ethylhexyl) idipate, di-(Z-ethylhexyl) azelate, di-(2-ethylhexyl) sebacate, di-(methylcyclohexyl) adipate and the like. Prefered solvents are the polar ethers such as diethylene glycol dimethyl ether and tetrahydrofuran.

To further illustrate my novel process and the compounds produced thereby, there are presented the following examples in which all parts and percentages are by weight unless otherwise indicated.

Example I Thirty-six parts of bis(cyclopentadienyl nickel) acetyl ene were dissolved in carbon disulfide solvent. Nitric oxide was then bubbled into the solution at room temperature and atmospheric pressure. As the reaction proceeded, the color of the solution changed from green to red. At this point, a sample of the solution was subjected to infrared analysis, and it was found that the solution contained a large quantity of cyclopentadienyl nickel nitrosyl. This was determined by comparison of the infrared spectrum of the solution with that of a standard solution containing an authentic sample of cyclopentadienyl nickel nitrosyl dissolved in carbon disulfide.

The solution was then vaporized and passed through a gas phase chromatographic column to determine the Example II A solution comprising one mole of bis (cyclopentadienyl nickel) propyne dissolved in benzene is charged to a cooled reaction vessel. There are then added 1.5 moles of nitric oxide, and the reaction mixture is agitated for 6 hours at a temperature of 0 C. and atmospheric pressure. The reaction product is then discharged, and excess solvent is stripped from the reaction product to leave an oily residue. The residue is dissolved in a 30:70 (volume ratio) benzene-petroleum ether mixture and chromatographed on alumina. The eluate is relieved of solvent 'by heating in vacuo, and the residue is fractionally distilled under reduced pressures to give a good yield of cyclopentadienyl nickel nitrosyl.

Example III A solution comprising 0.5 mole of 'bis(cyclopentadieny1 nickel) hexyne-3 in tetrahydrofuran is charged to a reaction vessel along with one mole of nitric oxide. The reaction mixture is heated at 25 C. for six hours with agitation. The product is then discharged, and a good yield of cyclopentadienyl nickel nitrosyl is obtained by fractional distillation at reduced pressures.

Example IV A solution comprising 1.5 moles of bis(cyclopentadienyl nickel) l-pentyne in toluene is charged to a reaction vessel along with two moles of sodium nitrite. The reaction mixture is heated with agitation for one hour at C. after which the reaction product is discharged. Fractional distillation of the reaction product under reduced pressures gives a good yield of cyclopentadienyl nickel nitrosyl.

Example V A solution comprising 1.0 mole of bis(cyclopentadienyl nickel) l-butyne in ethyl acetate is charged to a reaction vessel along with one mole of nitric oxide. After heating the reaction mixture for five hours at 30 C. with agitation, the reaction product is discharged, and a good yield of cyclopentadienyl nickel nitrosyl is obtained by means of fractional distillation at reduced pressure.

Example VI A solution comprising 0.33 mole of his (cyclopentadienyl nickel) phenylacetylene in diethyl ether solvent is charged to a reaction vessel along with 0.5 mole of nitric oxide. The reaction vessel is heated at 20 C. for seven hours with agitation of the reaction mixture after which the reaction product is discharged. Fractional distillation of the reaction product gives a good yield of cyclopentadienyl nickel nitrosyl.

Example VII A solution comprising 0.25 mole of bis(cyclopentadienyl nickel) perfluorobutyne-Z in n-hexane solvent is charged to a reaction vessel along with 0.33 mole of nitric oxide. The reaction mixture is heated at 50 C. for four hours with agitation of the reaction mixture. The reac tion product is then discharged, and cyclopentadienyl nickel nitrosyl is obtained therefrom by means of fractional distillation.

Example VIII A solution comprising 0.2 mole of bis(methylcyclo pentadienyl nickel) octyne-4 in carbon disulfide solvent is charged to a reaction vessel along with 0.25 mole of potassium nitrite. After heating with agitation for two hours at 40 C., the reaction product is discharged. On

fractional distillation of the reaction product, there is obtained in good yield a product, methylcyclopentadienyl nickel nitrosyl.

Example IX A solution comprising 0.1 mole of bis(indenyl nickel) hexyne-l dissolved in carbon disulfide is charged to a reaction vessel along with 0.15 mole of N-methyl-N- nitroso-p-toluene sulfonarnide. The reaction mixture is heated at 25 C. for six hours with agitation of the reaction mixture. The reaction product is then discharged, excess solvent is stripped therefrom, and the residue is dissolved in a benzene-petroleum ether mixture (30:70 volume ratio) and chromatographed on alumina. The eluate is then slowly cooled to yield indenyl nickel nitrosyl via fractional crystallization.

The compounds produced by my process can be employed as antiknock additives to liquid hydrocarbon fuels of the gasoline boiling range. The compounds can be used in the fuels by themselves or together with other additive components, such as scavengers, deposit modifying agents containing phosphorus and/ or boron, and also other antiknock agents, such as tetraethyllead, etc.

The compounds can :be added directly to the hydrocarbon fuels and the mixture subjected to stirring, mixing, or other means of agitation until a homogeneous fluid results. Alternatively, the compounds may be first made up into a concentrated fluid containing solvents, such as kerosene, toluene, hexane, and the like, as well as other additives such as scavengers, antioxidants and other antiknock agents, e.g., tetraethyllead and tetramethyllead. The concentrated fluids can then be added to the fuels.

When tested by the Research Method (Test Procedure D908-55, ASTM Manual of Engine Test Methods for Rating Fuels), the compounds produced by my process were found to be potent antiknocks. The test fuel, comprising 20 volume percent diisobutylene, 20 volume percent toluene, 20 volume percent isooctane and 40 volume percent n-hept-ane, had a Research octane number of 91.3. When cyclopentadienyl nickel nitrosyl was added to the fuel to give a concentration level of 1.0 gram of nickel per gallon, the Research octane number was increased to 93.8. At a concentration of 2.0 grams of nickel per gallon, the octane number Was increased to 95.0.

A further use for my compounds is in gas phase metal plating. In this application, the compounds are thermally decomposed in an atmosphere of a reducing gas such as hydrogen or a neutral atmosphere such as nitrogen to form metallic films on a substrate material. These films have a wide variety of applications. They may be used in forming conductive surfaces such as are employed in a printed circuit, in producing a decorative effect on a substrate material, or in applying a corrosionresistant coating to a substrate material.

The compounds of my invention also find application as additives to lubricating oils and greases to impart improved lubricity characteristics thereto. Further, my compounds may be incorporated in paints, varnish, printing inks, synthetic resins of the drying oil type, oil enamels and the like to impart improved drying characteristics to such compositions. Other important uses of my compounds include their use as chemical intermediates in the preparation of metal-containing polymeric materials. Also, some of the compounds of my invention can be employed in the manufacture of medicinals and other therapeutic materials, as well as in agricultural chemicals such as, for example, fungicides, defoliants, growth regulants, and the like.

A further utility for my compounds is as additives to distillate and residual fuels, e.g., home heater fuels, jet fuels and diesel fuels, to reduce smoke and soot formation on combustion of the fuels. Another use for my compounds is as additives to solid propellants to control burning rate.

Having fully defined my novel process, the compounds produced thereby, and their many utilities, I desire to be limited only within the lawful scope of the appended claims.

I claim:

1. Process comprising reacting a nitrosylating agent with a compound having the formula QCE CQ' CyNiNiCy in which Q and Q are selected from the class consisting of hydrogen and univalent alkyl, cycloalkyl, aralkyl, aryl, and alkaryl hydrocarbon radicals having from one to about 10 carbon atoms, and Cy and Cy are cyclomatic hydrocarbon radicals selected from the class consisting of the cyclopentadienyl radicals and hydrocarbon substituted cyclopentadienyl radicals having 6 to 13 carbon atoms which embody a ring of 5 carbon atoms having the general configuration found in cyclopentadiene.

2. The process of claim 1 wherein the nitrosylating agent is nitric oxide.

3. Process comprising reacting bis(cyclopentadienyl nickel) acetylene with nitric oxide in the presence of carbon disulfide solvent to yield cyclopentadienyl nickel nitrosyl.

4. Process comprising reacting a nitrosylating agent selected from the class consisting of nitric oxide, alkali metal nitrites and N-methyl-N-nitrosyl-p-toluene sulfonamide with a compound having the formula QCECQ'-CyNiNiCy' in which Q and Q are selected from the class consisting of hydrogen and univalent alkyl, cycloalkyl, aralkyl, aryl, and al-karyl hydrocarbon radicals having from one to about 10 carbon atoms, and Cy and Cy are cyclomatic hydrocarbon radicals selected from the class consisting of the cyclopentadienyl radical and hydrocarbon substituted cyclopentadienyl radicals having 6 to 13 carbon atoms which embody a ring of 5 carbon atoms having the general configuration found in cyclopentadiene.

5. The process of claim 4 wherein the nitrosylating agent is N-methyl-N-nitrosyl-p-toluene sulfonamide.

6. The process of claim 4 wherein the nitrosylating agent is an alkali metal nitrite.

References Cited in the file of this patent Piper et al.: Journal of Inorganic and Nuclear Chemistry 1955), vol. 1, pp. -174. 

4. PROCESS COMPRISING REACTING A NITROSYLATING AGENT SELECTED FROM THE CLASS CONSISTING OF NITRIC OXIDE, ALKALI METAL NITRITES AND N-METHYL-N-NITROSYL-P-TOLUENE SULFONAMIDE WITH A COMPOUND HAVING THE FORMULA 